3 The WHO European Centre for Environment and Health, Bonn, WHO Regional Office for Europe, coordinated the development of this publication. ABSTRACT This report presents the results of a systematic review of evidence of the health effects of black carbon (BC). Short-term epidemiological studies provide sufficient evidence of an association of daily variations in BC concentrations with short-term changes in health (all-cause and cardiovascular mortality, and cardiopulmonary hospital admissions). Cohort studies provide sufficient evidence of associations of allcause and cardiopulmonary mortality with long-term average BC exposure. Studies of short-term health effects suggest that BC is abetter indicator of harmful particulate substances from combustion sources (especially traffic) than undifferentiated particulate matter (PM) mass, but the evidence for the relative strength of association from long-term studies isinconclusive. The review of the results of all available toxicological studies suggested that BC may not be amajor directly toxic component of fine PM, but it may operate asauniversal carrier of a wide variety of chemicals of varying toxicity to the lungs, the body s major defence cells and possibly the systemic blood circulation. A reduction in exposure to PM 2.5 containing BC and other combustion-related PM material for which BC is an indirect indicator should lead to a reduction in the health effects associated with PM. Keywords AIR POLLUTION adverse effects SOOT toxicity INHALATION EXPOSURE adverse effects PARTICULATE MATTER analysis RISK ASSESSMENT ISBN: Address requests about publications of the WHO Regional Office for Europe to: Publications WHO Regional Office for Europe Scherfigsvej 8 DK 2100 Copenhagen Ø, Denmark Alternatively, complete an online request form for documentation, health information, or for permission to quote or translate, on the Regional Office web site (http://www.euro.who.int/pubrequest). World Health Organization 2012 All rights reserved. The Regional Office for Europe of the World Health Organization welcomes requests for permission to reproduce or translate its publications, in part or in full. The designations employed and the presentation of the material in this publication do not imply the expression of any opinion whatsoever on the part of the World Health Organization concerning the legal status of any country, territory, city or area or of its authorities, or concerning the delimitation of its frontiers or boundaries. Dotted lines on maps represent approximate border lines for which there may not yet be full agreement. The mention of specific companies or of certain manufacturers products does not imply that they are endorsed or recommended by the World Health Organization in preference to others of a similar nature that are not mentioned. Errors and omissions excepted, the names of proprietary products are distinguished by initial capital letters. All reasonable precautions have been taken by the World Health Organization to verify the information contained in this publication. However, the published material is being distributed without warranty of any kind, either express or implied. The responsibility for the interpretation and use of the material lies with the reader. In no event shall the World Health Organization be liable for damages arising from its use. The views expressed by authors, editors, or expert groups do not necessarily represent the decisions or the stated policy of the World Health Organization. Edited by: Rosemary Bohr. Cover design: Dagmar Bengs. Pictures: axepe, Imaginis, Ingo Bartussek, Jeanette Dietl, Kalle Kolodziej, mozzz, think4photop (Fotolia.com). Printed by: WarlichDruck RheinAhr GmbH.

5 page iv Acknowledgements This report was prepared by the Joint World Health Organization (WHO)/Convention Task Force on Health Aspects of Air Pollution according to the Memorandum of Understanding between the United Nations Economic Commission for Europe and the WHO Regional Office for Europe. The Regional Office thanks the Swiss Federal Office for the Environment for its financial support of the work of the Task Force. The Task Force on Health work is coordinated by the WHO European Centre for Environment and Health, Bonn. Convention on Long-range Transboundary Air Pollution

8 page vii Executive summary 1 Following decision 2010/2 of the Executive Body for the Convention on Long-range Transboundary Air Pollution (ECE/EB.AIR/106/Add.1, para 8(b)(i)), the Task Force on Health Aspects of Air Pollution working under the Convention conducted an assessment of the health effects of black carbon (BC) as a component of fine particulate matter (PM 2.5 ). The Task Force s discussion focused on formulating the conclusions presented below, on the basis of the working papers prepared for it and comments received from external reviewers. BC is an operationally defined term which describes carbon as measured by light absorption. As such, it is not the same as elemental carbon (EC), which is usually monitored with thermaloptical methods. Current measurement methods for BC and EC need to be standardized so as to facilitate comparison between the results of various studies. The main sources of BC are combustion engines (especially diesel), residential burning of wood and coal, power stations using heavy oil or coal, field burning of agricultural wastes, as well as forest and vegetation fires. Consequently, BC is a universal indicator of a variable mixture of particulate material from a large variety of combustion sources and, when measured in the atmosphere, it is always associated with other substances from combustion sources, such as organic compounds. The spatial variation of BC is greater than that of PM 2.5. Although, in general, ambient measurements or model estimates of BC reflect personal exposures reasonably well and with similar precision as for PM 2.5, the differences in exposure assessment errors may vary between studies and possibly affect estimates of risk. The systematic review of the available time-series studies, as well as information from panel studies, provides sufficient evidence of an association of short-term (daily) variations in BC concentrations with short-term changes in health (all-cause and cardiovascular mortality, and cardiopulmonary hospital admissions). Cohort studies provide sufficient evidence of associations of all-cause and cardiopulmonary mortality with long-term average BC exposure. Health outcomes associated with exposure to PM 2.5 or thoracic particles (PM 10 ) are usually also associated with BC (and vice versa) in the epidemiological studies reviewed. Effects estimates (from both short- and long-term studies) are much higher for BC compared to PM 10 and PM 2.5 when the particulate measures are expressed per unit of mass concentration (µg/m 3 ). Effect estimates are, however, generally similar per inter-quartile range in pollutant levels. Studies of short-term health effects show that the associations with BC are more robust than those with PM 2.5 or PM 10, suggesting that BC is a better indicator of harmful particulate substances from combustion sources (especially traffic) than undifferentiated PM mass. In multi-pollutant models used in these studies, the BC effect estimates are robust to adjustment for PM mass, whereas PM mass effect estimates decreased considerably after adjustment for BC. The evidence from longterm studies is inconclusive: in one of the two available cohort studies, using multi-pollutant models in the analysis, the effect estimates for BC are stronger than those for sulfates, but an opposite order in the strength of relationship is suggested in the other study. 1 Also published as part of Effects of air pollution on health. Report of the Joint Task Force on Health Aspects of Air Pollution (2011). Geneva, United Nations Economic and Social Council (ECE/EB.AIR/WG.1/2011/11) (http:// documents/2011/eb/wge/ece.eb.air.wg pdf, accessed 12 December 2011).

9 page viii There are not enough clinical or toxicological studies to allow an evaluation of the qualitative differences between the health effects of exposure to BC or to PM mass (for example, different health outcomes), of quantitative comparison of the strength of the associations or of identification of any distinctive mechanism of BC effects. The review of the results of all available toxicological studies suggested that BC (measured as EC) may not be a major directly toxic component of fine PM, but it may operate as a universal carrier of a wide variety of, especially, combustion-derived chemical constituents of varying toxicity to sensitive targets in the human body such as the lungs, the body s major defence cells and possibly the systemic blood circulation. The Task Force on Health agreed that a reduction in exposure to PM 2.5 containing BC and other combustion-related PM material for which BC is an indirect indicator should lead to a reduction in the health effects associated with PM. The Task Force recommended that PM 2.5 should continue to be used as the primary metric in quantifying human exposure to PM and the health effects of such exposure, and for predicting the benefits of exposure reduction measures. The use of BC as an additional indicator may be useful in evaluating local action aimed at reducing the population s exposure to combustion PM (for example, from motorized traffic).

10 page 1 Introduction The health effects of combustion-related air pollution indicated by black particles were identified decades ago, when the monitoring of black smoke (or British smoke BS) was a widespread method for air quality assessment in Europe. The evidence about the health effects of this pollution was used to recommend the first guidelines for exposure limits (then) consistent with the protection of public health (WHO, 1979). In the 1990s, BS was one of the indicators of air quality used, for example, in European time-series studies linking mortality with pollution (Katsouyanni et al., 2001). A recognition of the difficulties in standardizing BS measurements and an appreciation of the health effects of the non-black components of particulate matter (PM) attracted the attention of researchers and regulators to the mass concentration of inhalable or respirable fractions of suspended PM such as PM 10 and PM 2.5 (WHO Regional Office for Europe, 2000). BS is not addressed by air quality regulations and the intensity of BS monitoring has decreased. New scientific evidence has led to a recognition of the significant role of black particles (black carbon BC) as one of the short-lived climate forcers. Measures focused on BC and methane are expected to achieve a significant short-term reduction in global warming. If they were to be implemented immediately, together with measures to reduce CO 2 emissions, the chances of keeping the earth s temperature increase to less than 2 C relative to pre-industrial levels would be greatly improved (UNEP, 2011). The same measures would also directly benefit global health and food security. The synergy between action to address global warming and air quality has been noted by the parties to the Convention on Long-range Transboundary Air Pollution. Taking into account the conclusions of the report of the Ad Hoc Expert Group on Black Carbon (UNECE, 2010a), the Executive Body of the Convention decided to include consideration of BC, as a component of PM, in the revision process of the 1999 Gothenburg Protocol to Abate Acidification, Eutrophication and Ground-level Ozone (Gothenburg Protocol) (UNECE, 2010b). The Executive Body also requested the Joint Task Force on the Health Aspects of Air Pollution (the Task Force on Health) to look at the adverse effects on human health of black carbon as a component of PM 2.5. There is still no systematic comparison of health effects estimated using PM versus BC indicators. A WHO working group has acknowledged that the evidence on the hazardous nature of combustion-related PM (from both mobile and stationary sources) was more consistent than that for PM from other sources (WHO Regional Office for Europe, 2007). Grahame & Schlesinger (2010) reviewed the evidence of the effects of BC on cardiovascular health endpoints and concluded that it may be desirable to promulgate a BC PM 2.5 standard. Conversely, Smith et al. (2009) noted that although the results of their time-series meta-analysis suggest greater effects per unit mass of sulfate than BS, this distinction was less clear in the few studies that directly compared the estimated effects of both indicators. This indicates the need for a critical comparison of studies that have measured PM mass as well as BC particles. In response to the request from the Executive Body of the Convention, and in view of the lack of a systematic review of the accumulated evidence on the health effects of BC, the Task Force on Health launched the review by addressing the following specific questions.

11 page 2 1. What metrics have been used to estimate the health effects of exposure to BC? a. What are their respective strengths and weaknesses? b. How is personal exposure related to ambient levels? 2. What are the effects of BC exposure observed in epidemiological studies (health outcomes, exposure/response function)? a. What are the effects of short-term exposure? b. What are the effects of long-term exposure? c. Are they different qualitatively (for example, different health outcomes) and/or quantitatively from the effects of: i. PM 2.5 mass concentration ii. other measured components of PM 2.5? 3. What are the effects of BC in the human controlled exposure experiments? Are they different qualitatively (for example, different health outcomes) and/or quantitatively from the effects of: a. PM 2.5 mass concentration b. other measured components of PM 2.5? 4. What are the mechanisms of the effects of BC indicated by toxicological studies? a. Are they different from the mechanisms of effects attributed to undifferentiated PM 2.5 mass concentrations or other measured components of PM 2.5? b. Is there evidence supporting the thesis that (some of) the mechanisms are specific for BC? Leading the Task Force on Health, WHO invited selected experts to prepare concise background papers summarizing evidence corresponding to each of the above questions. The experts signed the WHO declaration of interest, assuring the absence of any conflicts of interests related to their contributions to the assessment. The papers were based on a systematic review of the literature, with relevant documentation of the protocol of the review and of the evidence reviewed (see Annex 1). The conclusions of the review were prepared by WHO and the authors of the background papers based on the papers. The summary also rated the quality of the evidence supporting each conclusion based on the approach used in the WHO Indoor air quality guidelines (WHO Regional Office for Europe, 2010, p 6). Both the papers and the summary were subject to review by another group of experts, and their comments were made available to all members of the Task Force on Health in advance of the 14th Task Force Meeting, held in Bonn on May 2011 (list of participants in Annex 2). The discussion at the Meeting focused on finalizing the summary assessment, which has been published in the Task Force Report (UNECE, 2011). This summary also forms the Executive Summary of this report. The background papers presented in this report were revised after the Task Force Meeting, based on the comments of the reviewers before and at the Meeting.

13 page 4 1. Metrics used to estimate the exposure to BC in health studies: strengths and weaknesses Raimo O Salonen Introduction There are several types of measurement method and commercial instrument available for continuous, semi-continuous and integrated filter sample-based optical and thermal-optical measurements of aerosol parameters reflecting combustion-derived char, soot, black carbon or elemental carbon contents in PM. The concentrations of these carbonaceous material are low or moderate (close to source) in atmospheric PM, and much higher in emissions from common combustion sources (diesel engines, power plants or ship engines using heavy oil, or small residential heaters using wood or other biomass). The following are explanations of the bolded terms in common language according to Han et al. (2007; 2010). Char is defined as carbonaceous material obtained by heating organic substances and formed directly from pyrolysis, or as an impure form of graphitic carbon obtained as a residue when carbonaceous material is partially burned or heated with limited access of air (typical of burning vegetation and wood in small residential heaters). Soot is defined as only those carbon particles that form at high temperature via gas-phase processes (typical of diesel engines). Black carbon (BC) refers to the dark, light-absorbing components of aerosols that contain two forms of elemental carbon. Elemental carbon (EC) in atmospheric PM derived from a variety of combustion sources contains the two forms char-ec (the original graphite-like structure of natural carbon partly preserved, brownish colour) and soot-ec (the original structure of natural carbon not preserved, black colour) with different chemical and physical properties and different optical light-absorbing properties. A thermal optical reflectance method can be applied to differentiate between char-ec and soot-ec according to a stepwise thermal evolutional oxidation of different proportions of carbon under different temperatures and atmosphere (more details under Measurement methods of the dark component of PM, below). The health significance of the separate char-ec and soot-ec is not known. In general, EC or BC are regarded as having negligible toxic effects on human and animal lungs in controlled studies and on airway cells such as macrophages and respiratory epithelial cells. Instead, it has been suggested that they exert an indirect key role in toxicity as a universal carrier of toxic semi-volatile organics and other compounds co-released in combustion processes or attached to their surface during regional and long-range transport (see Chapter 4). The optimal combustion of fuel at high temperature, such as the current low-sulfur fossil diesel fuel in modern diesel engines, results in the emission of large numbers of very small soot particles (aerodynamic diameter 1 5 nm) that rapidly grow in size ( nm) in the tailpipe by coagulation to form aggregated chains, and further by condensation of the simultaneously released semi-volatile organic substances on their surfaces in the atmosphere. The speed of growth depends on air temperature, sunlight, concomitant oxidants, etc. (D Anna, 2009).

14 page 5 The burning of solid fuels, such as wood and coal, is usually not optimal, especially in small residential heaters, since there is, to a varying degree, incomplete smouldering combustion due to the relative shortage of oxygen. Subsequently, the aerodynamic diameter of emitted PM in flue gas becomes larger ( nm) than in the case of diesel oil combustion in car engines, because in addition to thermochemically-formed EC there are incompletely burnt tar-like organics attached to it. As with diesel car PM, these emitted PM continue to grow in the atmosphere by condensation of semi-volatile organics on their surface. The combustion of solid fuels, such as wood and coal, tends to produce much larger amounts of semi-volatile organics than combustion of low-sulfur diesel oil (Naeher et al., 2007; Kocbach Bolling et al., 2009). While ageing in the atmosphere for several hours or days, the combustion-derived particles become even larger (up to 1 µm in diameter) because inorganic salts originating from both NO 2 and SO 2, together with atmospheric water, attach to the surfaces of hygroscopic carbonaceous particles. Taking into account the wide variations in the formation and composition of combustion-derived PM, and the fact that some of its chemical composition is known to exert not only light-absorbing (soot/bc/ec) but also considerable light-scattering (organics, inorganics) properties, it is no surprise that many indirect optical measurement techniques and thermal optical analysis methods, which have been used for many years in air quality measurements by aerosol and by health scientists, have proved to give only a rough proxy of the BC or EC concentration in ambient air without instrument-specific corrective measures. Some methods have also had instrument-specific technical problems during operation in large methodological inter-comparison studies conducted by the leading aerosol scientists in Asia, Europe and the United States (Müller et al., 2011; Chow et al., 2009; Reisinger et al., 2008; Kanaya et al., 2008; Hitzenberger et al., 2006). Measurement methods of the dark component of PM Combustion-derived soot and char (in practice, their dark components) have been determined in epidemiological studies by the following techniques: light reflectance from (absorbance (Abs), BS) or light transmission through (basis of measurement of BC) integrated PM samples usually collected at 24-hour intervals on thin cellulose fibre filter or other filter material, followed by conversion of the optical measurement units to mass-based units; real-time photometers measuring light absorption of PM sample spots (BC) at 1 5 minute intervals and automatically giving readings in mass-based units; chemical determination of EC and organic carbon (OC) using thermal optical analysis methods either semi-continuously with mass-based readings given every 30 minutes to 3 hours, or from integrated PM samples collected at 24-hour intervals on quartz filters (Müller et al., 2011; Janssen et al., 2011; Chow et al., 2009). The absorption coefficient of PM and BS measured with a reflectometer and BC measured with an optical transmissometer are metrics that are based on the blackness of aerosol material collected on a filter. Light is focused on the filter sample and the amount of light reflected or transmitted is measured. For BS and Abs, the amount of reflected light is converted into PM mass units (OECD standard) (OECD, 1964) or the black smoke index ISO standard 9835:1993 (ISO, 1993), whereas in the BC method the light transmitted is converted to represent the mass of EC. BS measurement has been used in Europe since the 1920s, when urban air pollution was dominated in many places by smoke from coal combustion. Although BS and Abs determinations are expressed in µg/m 3, there is no clear relationship to PM mass, as conversion

15 page 6 of the optical measurement results into mass units depends on location, season and type of combustion particle. Absorption photometers for real-time application have been available since the 1980s. These are filter-based instruments that measure at intervals of one to five minutes the changes in transmittance through a fibrous filter tape as particles are deposited. The complex relationship between changes in light transmission and aerosol absorption and scattering on the filter requires an adequate calibration of these methods, including the selection of an effective wavelength for a valid absorption co-efficient, determination of filter spot size and characterization of the aerosol flow (Müller et al., 2011). Algorithms have been published for correcting artefactual enhancement of light absorption by filter-loading, back-scattering, and multiple scattering caused by PM and the filter matrix in connection with aethalometers and particle soot absorption photometers. The multi-angle absorption photometer is the only real-time absorption photometer that corrects for these artefacts by design (Müller et al., 2011; Chow et al., 2009) (Table 1). Thermal optical methods are based on OC and EC removed from sampling substrates (such as quartz-fibre filter) by volatilization and/or combustion at selected temperatures, and by conversion of the released gases to carbon dioxide (CO 2 ) or methane (CH 4 ). This is followed by infrared absorption (CO 2 ) or flame ionization (CH 4 ) detection. EC is not volatile and is only released by oxidation. Most of the atmospheric OC tends to evolve at temperatures 550 C in pure helium atmosphere and, thus, it can be separated from EC that needs to be oxidized in helium 98%/oxygen 2% at temperatures 550 C. Heating in an inert helium atmosphere, however, causes certain OC compounds to pyrolyse or char, thereby exaggerating the atmospheric EC in the sample. In thermal optical carbon analysis, this can be corrected by simultaneous measurement of thermal optical reflectance (TOR) or thermal optical transmittance (TOT). Although the principles of thermal methods appear to be similar, they contain variations with respect to: location of the temperature monitor (thermocouple) relative to the sample, analysis atmospheres and temperature ramping rates; temperature plateaus; residence time at each plateau; optical pyrolysis monitoring configuration; carrier gas flow through or across the sample; and oven flushing conditions. Chow et al. (2005; 2009) and Han et al. (2007; 2010) have done a lot of development and comparisons of thermal optical methods. Currently, their Interagency Monitoring of Protected Visual Environments (IMPROVE_A) thermal optical reflectance protocol (IMPROVE_A_TOR) seems the best thermal optical method for separating various OC fractions from each other as well as for separating char-ec from soot-ec (Table 1). Comparison of the optical measurement methods with each other and with more sophisticated methods BS/PM 10 ratios measured with the reflectometer have varied widely in Europe and many times exceeded one in some locations (Hoek et al., 1997), as the Abs units are converted to BS values in µg/m 3 by using a constant conversion factor. This is a major source of bias, because the greatly varying OC/EC ratio in PM affects Abs due to scattering of light from combustion-type organic material. A typical OC/EC ratio in urban traffic environments is two, while the OC/EC ratio can be five in rural background areas with more prevalent biomass combustion. Thus, BS data from different types of site or from different seasons or from decade-long time-series at the same site are not comparable. BS measurement should always be accompanied by local calibration of the conversion factor from Abs units to BS values in µg/m 3 on the basis of the OC/EC ratio in PM (Schaap & Denier van der Gon, 2007).

16 page 7 Table 1. Summary of methodological aspects in relation to measurement of light Abs, BS, BC or EC in atmospheric PM PM metrics General information Methodological principle Strengths and limitations PM Abs, BS, BC. Cheap and simple measurements from integrated filter samples Reflectometer. Collection of usually 24-hour PM samples on Whatman paper filter at sampling flow volume of 2±0.2 m 3 /day, absorption coefficient measured from PM on filter using simple reflectometer consisting of a light source and a detector (ISO 9835:1993 (E)). Originally, there was an OECD standard (1964) for BS measurement from total suspended particulate samples. Optical transmissometer. This portable instrument can perform rapid, non-destructive BC determination from PM material collected on different types of filter (diameter 25mm, 37 mm or 47mm). The instrument has a movable tray with two filter-holder slots, one inside and the other outside. The outside holder is used to measure light attenuation through the sample filter, while a simultaneous measurement is made through the reference (blank) filter placed in the inside holder. The analysis time for an individual measurement is less than one minute. Reflectometer. Analogue or digital readout of either percentage reflectance (linear scale, recommended range 35 95%) or absorption coefficient (logarithmic scale, recommended range ) that can be transformed into abs index (ISO 9835, 1993). According to the OECD standard (1964), there is a conversion of the reflectance data into gravimetric units (µg/m 3 ). The same has been done with absorption by using a fixed conversion factor: 1unit of Abs equals an increase of 10 µg/m 3 BS (Roorda-Knape et al., 1998). Optical transmissometer. The OT-21 is based onthe optics used in some aethalometer models. It measures the transmission intensity of light at 880 nm and 370 nmpassing through a particle-loaded filter and determines the attenuation of light compared to the intensity of ablank filter. Reflectometer. Standardized, traditional and cheap method; long time-series in several central European countries according to the OECD (1964) specifications. Baseline reflectance of unused filters may vary from batch to batch. Scattering of light from PM sample rich in organics or due to some inorganics results in biased reflectance values. BS (R 2 = ) and absorption (R 2 = ) methods have had high correlations with thermal optical EC, but the slopes of the association show wide variations (BS 10 µg/m 3 equals EC µg/m 3 ) (Janssen et al., 2011). A study in the Netherlands showed that BS readings depended on the OC/EC ratio in ambient air (r 2 =0.85 for urban sites and r 2 =0.75 for rural sites) and the slopes of association varied with the type of measurement site and local combustion sources (Schaap & Denier van der Gon, 2007). Optical transmissometer. The results obtained from three different types of site in the United States (New York State) and one site inturkey showed that the relationships between BC values obtained from the OT- 21 and thermal optical BC values from a semi-continuous carbon analyser were linear. The slopes for the data from the sites varied from 0.75 to 1.02 (r 2 = 0.44 to 0.88), which was mainly attributed to the different chemical composition of aerosols as well as their age in the atmosphere. When the data were combined and plotted as monthly average BC, the two methods showed excellent agreement (slope 0.91, r 2 =0.84) (Ahmed et al., 2009). BC. Absorption photometers for real-time application (averageing time 1 5 minutes). Real-time absorption photometers. Filterbased instruments measure the change of transmittance through a fibrous filter tape as Aethalometer (Hansen, Rosen & Novakov, 1984). Offered in different configurations. Multispectral ( nm) absorption coefficients provide insight into chemical composition in PM sample. PM Unit-to-unit variability between similar instruments. Up to 30% for PSAPs and aethalometers, while less than 5% for multiangle absorption photometers. Reasons for the high variability

17 page 8 PM metrics General information Methodological principle Strengths and limitations particles are deposited. The complex relationship between change in light transmission and aerosol absorption and scattering on the filter requires acalibration of these methods (effecttive wavelength for valid absorption coefficient, determination of filter spot size, aerosol flow characterization) (Muller et al., 2011). Published algorithms for correction of artefactual enhancement of light absorption by filter-loading, backscattering and multiple scattering by PM and the filter matrix in connection with aethalometers and particle soot absorption photometers. Multi-angle absorption photometers correct by design for these artefacts (Muller et al., 2011; Chow et al., 2009; Kanaya et al., 2008). collection on quartz-fibre filter tape, flow rate 6.7 litres/ minute and averaging time 5 minutes. Particle soot absorption photometers (Bond, Anderson & Campbell, 1999). Absorption coefficients measured at variable wavelengths ( nm). Dependence of response on PM size and cross-sensitivity to particle scattering that can becontrolled by simultaneously measured nephelometer data. PMcollection on glassfibre filter tape, typical flow rate 0.5 1litre/minute and averaging time 3 seconds. Multi-angle absorption photometers (Petzold & Schonlinner, 2004). Measures radiation transmitted through and scattered back from a PM-loaded filter. A two-stream radiative transfer model used to minimize the cross-sensitivity to particle scattering. Usual emission at wavelength 670 nm. PM collection on glass-fibre filter tape, flow rate 16.7 litres/minute. Minimum detection limit as specified by the manufacturer isbc<0.1 μg/m 3 with an averaging time of 2 minutes (Chow et al., 2009). were identified as variations in sample flow and spot size and as cross-sensitivity to PM scattering (Müller et al., 2011). Correlations in absorption coefficients between different instruments. Particle soot absorption photometers versus multiangle absorption photometers (R2= ), aethalometers versus multi-angle absorption photometers (R2=0.96) (Muller et al., 2011). In a campaign in the United States (Fresno supersite), agreement inbcbetween corrected aethalometers (660nm) and multi-angle absorption photometers (670 nm) was within 1%. BC concentrations determined with thesemi-continuous carbon analyser were highly correlated (R 0.93) but were 47% and 49% lower than BC measured with aethalometers and multi-angle absorption photometers, respectively (Chow et al., 2009). ElevatedBC-to-ECratios with multiangle absorption photometers possibly connected to biomassderived abundant OC fraction volatilizing at high temperatures (Reisinger etal., 2008, Kanaya et al., 2008) and to aged BC with coating by transparent materials causing alensing effect in optical measurements (Kanaya et al., 2008). Comparison of absorption photometers with more advanced measurement techniques Photoacoustic instrument. This is regarded as an unofficial reference or benchmark method for BC. Photoacoustic instrument (Arnott et al., 1999). PM are drawn into a cavity and illuminated by alaser with the desired wavelength modulated at the resonant frequency of the cavity. The heating and cooling of the particle inresponse to the absorbed light creates a sound wave that is detected by a microphone. The intensity of the acoustic wave is related to PM light absorption by calibration with NO 2 absorption. Typical flow rate 1 litre/minute and averaging time 3 4 seconds. Comparison with photoacoustic instrument. In the Fresno supersite campaign, uncorrected PM light absorptions with aethalometers were times, and with PSAP times, higher than those with a photoacoustic instrument. After applying published algorithms to correct for the artefacts, the adjusted values for aethalometers were 24 69% higher, and for PSAP 17 28% higher, than those for the photoacoustic instrument. The greater differences were at higher wavelengths. Multi-angle absorption photometers gave 51% higher PM light absorption than the photoacoustic instrument. However, all uncorrected and corrected aethalometer, particle soot absorption photometer and multi-angle absorption photometer data were highly corre-

18 page 9 PM metrics General information Methodological principle Strengths and limitations lated (R 0.95) with photoacoustic instrument data (Chow etal., 2009). Comparison withthermal optical methods. The average differences between BC concentration by adjusted 7-AE (660 nm) and multi-angle absorption photometers (670 nm) versus EC concentration by IMPROVE_A_TOR were 0 and 6%, respectively. The BC analysed by semi-continuous carbon analyser using the National Institute for Occupational Safety and Health (NIOSH) 5040_TOT protocol (660 nm) was 47% lower than the EC analysed by IMPROVE_A_TOR. In all comparisons, correlations were r 0.87 (Chow et al., 2009). Comparisons between EC/OC thermal optical methods IMPROVE_A_TOR/TOT protocol. PM collected on a quartz-fibre filter at ambient temperature and pressure is subject to thermal carbon analysis following the IMPROVE_A protocol using the DRI Model 2001 thermal/optical carbon analyser. The correction for pyrolysed OC is done by monitoring laser reflectance (TOR) or laser transmittance (TOT). STN TOR/TOT protocol. PM collection the same as above. Thermal/optical transmission/reflectance analysis applied to the US PM 2.5. Speciation Trends Network (STN). Filter transmittance is monitored to split OC and EC (STN_TOT). With the DRI Model 2001 thermal/optical carbon analyser, reflectance can also be recorded during the analyses (STN_TOR). Semi-continuous carbon analyser_tot. PM collected onthe quartz fibre filter tape is IMPROVE_A_TOR/TOT. The evolved carbon is converted toco 2and reduced to CH 4 that is detected using a flame ionization detector. Pure helium is used as the carrier gas in stepwise rising temperatures from 30 C to550 C or 580 C to separate various OC fractions from eachother. The separation of various EC fractions from each other is done in helium 98%/oxygen 2% at temperatures from 550 C or 580 C to 800 C or 840 C: char-ec separated from soot-ec at around 700 C or 740 C (Chow et al., 2009; Han et al., 2007; Chow et al., 2005). Reports 24-hour concentrations of EC and OC (including their sub-fractions), total carbon and PM light absorption. STN TOR/TOT. Pure helium isused as the carrier gas in stepwise rising temperatures from 30 C to 900 C to separate various OC fractions. Helium 98%/oxygen 2% is applied to EC fractions at temperatures from 600 C to 920 C. Reports 24-hour concentrations of EC, OC and total carbon. Semi-continuous carbon analyser_ TOT. Evolved CO 2 is analysed by the non-dispersive infrared sensor. In the NIOSH 5040 protocol. Pure helium is used as the carrier gas in stepwise rising temperatures from 30 C to 840 C for various OC fractions. Helium 98%/oxygen 2% is applied to EC fractions at tempe- IMPROVE_A_TOR/TOT. The residence time ( seconds) at each temperature plateau in the IMPROVE_A protocol is flexible to achieve well-defined carbon fractions, and depends on when the flame ionization detector signal returns to the baseline (Chow et al., 2005; 2009). STN TOR/TOT and NIOSH 5040_TOT. The STN protocol has short and fixed residence times ( seconds), as does the NIOSH 5040 protocol ( seconds) for each temperature plateau. They cannot, therefore, report distinguishable carbon fractions. Comparison between thermal optical protocols. In the Fresno supersite study, 24-hour EC concentration by TOR was 23% higher than EC by TOT following the IMPROVE_A protocol, and 29% higher following the STN protocol. These differences were smaller when TOR was used to determine the OC/EC split. EC by STN_TOR was 10% lower than by IMPROVE_A_TOR. NIOSH 5040_TOT of the semicontinuous carbon analyser gave 45% lower integrated 24-hour EC concentration than that by IMPROVE_A_TOR. In all cases, the pairwise correlations were r 0.87 (Chow et al., 2009).

19 page 10 PM metrics General information Methodological principle Strengths and limitations subjected to thermal optical analysis following the NIOSH 5040_TOT protocol. Typical flow rate 8.5 litres/minute and averaging time 1hour. Used as afield instrument for air quality and health studies. ratures from 550 C to 850 C. Laser transmittance (TOT) is used to correct for pyrolysis. During the PM collection phase, light transmission through the filter is monitored to quantify BC similarly to aethalometers. All measurements at 660 nm. Reports 1-hour concentrations of BC, EC, OC and total carbon for ambient conditions. The variability in the chemical composition of BC aerosol at different locations also biases the BC data of optical transmissometers. It has been suggested that these should be calibrated with the help of more sophisticated and reliable measurement techniques using statistically significant numbers of samples for the specific sites (Ahmed et al., 2009). As with reflectometers, however, controlling the measurement bias by local calibrations may not be easy, because the OC/EC ratio in PM can also vary with the season and with day-to-day temperatures at the same site due to variations in biomass combustion for residential heating. Aerosol scientists have produced valuable information about the type and quantity of sources of measurement error in relation to absorption photometers for real-time application (Müller et al., 2011; Chow et al., 2009; Reisinger et al., 2008; Kanaya et al., 2008; Hitzenberger et al., 2006). In fact, the use of filter-based instruments to derive information on aerosol light Abs and BC is a matter of debate (Müller et al., 2011), as is the use of older optical measurements of BS and Abs (see Janssen et al., 2011). Currently, there is no generally accepted standard method to measure BC or EC. It has, however, been possible to make comparisons of several filter-based instruments of aerosol light Abs with more sophisticated instruments such as the photoacoustic analyser (Chow et al., 2009). Several workshops have been conducted to investigate the performance of individual instruments, for example, two workshops with large sets of aerosol absorption photometers in 2005 and The data from these instruments have been corrected using existing methods, but still the most recent inter-comparison has shown relatively broad variations in responses to PM light absorption in connection with some instruments (Müller et al., 2011). Significant biases associated with filter-based measurements of PM light absorption, BC and EC are methodspecific. Correction of these biases must take into account the variations in aerosol concentration, composition and sources (Chow et al., 2009). The key results from the comparisons of the real-time optical measurement methods with each other and with more sophisticated methods of measuring BC and EC, and from the comparisons of BS and Abs with EC (Janssen et al., 2011) are summarized in Table 1. The literature search and the criteria for selection of the literature cited are described in Annex 1. Conclusions BC is an operationally defined term, which describes carbon as measured by light absorption. As such, it is not the same as EC, which is usually monitored with thermal-optical methods. Despite intensive efforts during the past 20 years, there are no generally accepted standard methods to measure BC or EC in atmospheric aerosol. While most of the measurement methods of BC or

20 page 11 EC seem to be well-correlated, biases in filter-based light absorption and thermal optical carbon measurements need to be identified and corrected for accurate determination of aerosol light absorption, BC and EC in different environments. Variations in the OC/EC ratio bias filter-based PM light absorption in addition to other artefacts. The multi-angle absorption photometer is currently the only type of real-time absorption photometer that corrects for these biases and artefacts of BC measurement by design. However, aethalometer data can be corrected using published algorithms. The IMPROVE_A protocol in thermal optical carbon analyser, equipped with laser reflectance (TOR) to correct for pyrolysed OC, currently seems to be the most reliable method to measure OC and EC concentrations from atmospheric PM in integrated filter samples. The flexible residence time ( seconds) at each temperature plateau also enables the measurement of well-defined OC and EC sub-fractions, which may be useful in PM source analysis. At their best in a field campaign, the 24-hour concentrations of BC by multi-angle absorption photometer and from corrected aethalometer data have been nearly equal to the 24-hour EC concentration measured by IMPROVE_A_TOR. Current methods of measuring BC and EC need standardization to facilitate comparison between various study results. References Ahmed T et al. (2009). Measurement of black carbon (BC) by an optical method and a thermal-optical method: intercomparison for four sites. Atmospheric Environment, 43(40): Arnott WP et al. (1999). Photoacoustic spectrometer for measuring light absorption by aerosol: instrument description. Atmospheric Environment, 33: Bond TC, Anderson TL, Campbell D (1999). Calibration and intercomparison of filter-based measurements of visible light absorption by aerosols. Aerosol Science and Technology, 30: Chow JC et al. (2005). Refining temperature measures in thermal/optical carbon analysis. Atmospheric Chemistry and Physics, 5(4): Chow JC et al. (2009). Aerosol light absorption, black carbon, and elemental carbon at the Fresno Supersite, California. Atmospheric Research, 93: D Anna A (2009). Combustion-formed nanoparticles. Proceedings of the Combustion Institute, 32: Han YM et al. (2007). Evaluation of the thermal/optical reflectance method for discrimination between char- and soot-ec. Chemosphere, 69: Han YM et al. (2010). Different characteristics of char and soot in the atmosphere and their ratio as an indicator for source identification in Xi an, China. Atmospheric Chemistry and Physics, 10: Hansen ADA, Rosen H, Novakov T (1984). The aethalometer an instrument for the real-time measurement of optical absorption by aerosol particles. Science of the Total Environment, 36: Hitzenberger RA et al. (2006). Intercomparison of thermal and optical measurement methods for elemental carbon and black carbon at an urban location. Environmental Science & Technology, 40: Hoek G et al. (1997). Wintertime PM 10 and black smoke concentrations across Europe: results from the PEACE study. Atmospheric Environment, 31: ISO (1993). ISO standard 9835:1993 (E). Ambient air determination of a black smoke index. Geneva, International Organization for Standardization. Janssen NAH et al. (2011). Black carbon as an additional indicator of the adverse health of airborne particles compared to PM 10 and PM 2.5. Environmental Health Perspectives, 119: Kanaya Y et al. (2008). Mass concentrations of black carbon measured by four instruments in the middle of Central East China in June Atmospheric Chemistry and Physics, 8:

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